3-aminophenyl-3-(phenylsulfonyl)-1,1-bis(aminophenyl/indol-3-yl) propenes

ABSTRACT

1-A-1-B-3-(2-R 2  -4-N-R-N-R 1  -aminophenyl)-3-(-4-R 3  -phenylsulfonyl)prop-1-ene useful as color formers, particularly in transfer imaging, pressure-sensitive and thermal-responsive carbonless duplicating systems, are prepared by the interaction of the corresponding 1-A-1-B-ethene with the appropriate 2-R 2  -4-N-R-N-4 1  -benzaldehyde and the appropriate 4-R 3  -benzenesulfinic acid in the presence of an acidic catalyst.

This application is a division of application Ser. No. 056,169, filedJune 1, 1987, now U.S. Pat. No. 4,795,736.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention described herein relates to novel compounds classified inthe field of organic chemistry as propenes, useful as color-formingsubstances, particularly in the art of transfer imaging,pressure-sensitive and thermal-responsive carbonless duplicating; totransfer imaging systems containing said compounds; topressure-sensitive and thermal-responsive carbonless duplicating systemscontaining said compounds and to processes for preparing said propenes.

2. Information Disclosure Statement

Several classes or organic compounds of widely diverse structural typesare known to be useful as colorless precursors for transfer imagingsystems. Among the more important classes, there may be named leuco-typedyestuffs such as: phthalides, for example, crystal violet lactone,Malachite green lactone; fluorans, for example,3-dialkylamino-7-dialkylaminofluoran, 3-dimethylamino-6-methoxyfluoran;phenothiazines, for example, benzoyl leuco methylene blue; Rhodamines,for example, Rhodamine B-anilinolactone; and spiro-dinaphthopyrans, forexample, 3-methyl-spiro-dinaphthopyran. The classes of organic compoundslisted above also generally find utility in pressure-sensitive andthermal-responsive carbonless duplicating systems.

Typical of the transfer imaging systems, is the system described in U.S.Pat. No. 4,399,209, which issued Aug. 16, 1983. In this patent, atransfer imaging system is disclosed wherein images are formed byimage-wise exposing a layer comprising a chromogenic andpressure-rupturable material containing as an internal phase, aphotosensitive composition. In this system, the chromogenic material isencapsulated with the photosensitive compound. Upon exposure to filteredU.V. or blue light in the wavelength range of 380 to 480 nanometers, acertain portion of the capsules will harden. The capsules in which theinternal phase has remained liquid are ruptured and the chromogenicmaterial is image-wise transferred to a developer or copy sheet wherethe chromogenic material reacts with a developer to form an image.

Typical of the many commercially accepted pressure-sensitive andthermal-responsive carbonless copy systems are those described in U.S.Pat. Nos. 2,712,507; 2,800,457; 3,041,289; and 4,000,087, which issuedJuly 5, 1955; July 23, 1957; June 26, 1962; and Dec. 28, 1976,respectively.

Many of the color formers in the prior art suffer one or moredisadvantages such as low tinctorial strength, low resistance tosublimation, low susceptibility to copiability of the color-developedimages in standard office copying machines, for example, a xerographictype of copier, poor image stability in the presence of light, i.e., theproduct image fades losing intensity or changes to a less acceptablecolor, and low solubility in common organic solvents. The latterdisadvantage requires the use of specialized and expensive solvents inorder to obtain microencapsulated solutions of sufficient concentrationfor use in pressure-sensitive copying systems and transfer imagingsystems.

The following items to date appear to constitute the most relevant priorart with regard to the instant invention.

Ricoh KK-owned Japanese Patent Publication 60,231,766, which waspublished Oct. 18, 1985, discloses compounds having the structuralformula ##STR1## wherein R¹ -R⁴ =lower alkyl; and R⁵ =H or lower alkyl.The compounds are disclosed as being useful as color formers forheat-and pressure-sensitive recording paper capable of being read by anoptical reader.

Ricoh KK-owned Japanese Patent Publication 60,230,890, which waspublished Oct. 16, 1985, discloses compounds having the structuralformula ##STR2## wherein R¹ -R⁴ are H or (un)substituted alkyl; R⁵ andR⁶ are H or (un)substituted phenyl; R⁷ is (un)substituted alkyl or(un)substituted phenyl.

The compounds are disclosed as being useful as color formers for heat-and pressure-sensitive recording paper capable of being read by anoptical reader.

SUMMARY OF THE INVENTION

In its composition of matter aspect, the invention relates to certain1-A-1-B-3-(2-R² -4-N-R-N-R¹ -aminophenyl)-3-(4-R³-phenylsulfonyl)prop-1-enes useful in transfer imaging systems,pressure-sensitive and thermal-responsive carbonless duplicatingsystems.

In its process aspect, the invention relates to a process for producing1-A-1-B-3-(2-R² -4-N-R-N-R¹ -aminophenyl)-3-(4-R³-phenylsulfonyl)prop-1-enes which comprises interacting thecorresponding 1-A-1-B-ethene with the appropriate 2-R² -4-N-R-N-R¹-benzaldehyde and the appropriate 4-R³ -benzenesulfinic acid in thepresence of an acidic catalyst.

The present invention provides in one of its article of manufactureaspects, a substrate for use in transfer imaging systems comprising asupport sheet containing as a color-forming substance, 1-A-1-B-3-(2-R²-4-N-R-N-R¹ -aminophenyl)-3-(4-R³ -phenylsulfonyl)prop-1-enes.

The present invention provides in the second of its article ofmanufacture aspects, a substrate for use in pressure-sensitive andthermal-responsive carbonless duplicating systems comprising a supportsheet containing as a color-forming substance, 1-A-1-B-3-(2-R²-4-N-R-N-R¹ -aminophenyl)-3-(4-R³ -phenylsulfonyl)prop-1-enes.

DETAILED DESCRIPTION INCLUSIVE OF THE PREFERRED EMBODIMENTS

More specifically, this invention in one of its composition of matteraspects, resides in the novel 1-A-1-B-3-(2-R² -4-N-R-N-R¹-aminophenyl)-3-(4-R³ -phenylsulfonyl)prop-1-enes having the formula##STR3## wherein A represents a moiety selected from the groupconsisting of ##STR4## B represents a moiety selected from the groupconsisting of ##STR5## in which Z represents hydrogen or --NR¹¹ R¹² ; R,R⁵ and R¹¹ independently represent hydrogen; non-tertiary C₁ to C₁₆alkyl; phenyl; phenyl substituted by one or two of non-tertiary C₁ to C₄alkyl, non-tertiary C₁ to C₄ alkoxy, nitro or halo, benzyl; or benzylsubstituted in the benzene ring by one or two of non-tertiary C₁ to C₄alkyl, non-tertiary C₁ to C₄ alkoxy, nitro or halo; R¹, R⁶ and R¹²independently represent non-tertiary C₁ to C₁₆ alkyl; R², R⁴ and R¹⁰independently represent hydrogen, non-tertiary C₁ to C₁₆ alkyl,non-tertiary C₁ to C₈ alkoxy, nitro or halo; R³ represents hydrogen,non-tertiary C₁ to C₁₆ alkyl, non-tertiary C₁ to C₄ alkoxy, nitro orhalo; R⁷ and R¹³ independently represent hydrogen; non-tertiary C₁ toC₁₆ alkyl unsubstituted or substituted by non-tertiary C₁ to C₁₆ alkoxy,phenoxy, phenyl, phenyl substituted by one or two of non-tertiary C₁ toC₄ alkyl, non-tertiary C₁ to C₄ alkoxy, nitro or halo; R⁸ and R¹⁴independently represent hydrogen, non-tertiary C₁ to C₄ alkyl or phenyl;R⁹ and R¹⁵ independently represent one or two of hydrogen, non-tertiaryC₁ to C₄ alkyl, non-tertiary C₁ to C₄ alkoxy, nitro or halo; and whereinR and R¹ together with the nitrogen represent piperidinyl orpyrrolidinyl.

In a first particular embodiment within the ambit of the composition ofmatter aspect are the novel 1-(2-R⁴ -4-N-R⁵ -N-R⁶ -aminophenyl)-1-(2-R¹⁰-4-Z-aminophenyl)-3-(2-R² -4-N-R-N-R¹ -aminophenyl)prop-1-enes ofFormula I wherein A is (2-R⁴ -4-N-R⁵ -N-R⁶ -aminophenyl) and B is (2-R¹⁰-4-Z-aminophenyl) having the formula ##STR6## in which Z, R, R¹, R², R³,R⁴, R⁵, R⁶, and R¹⁰ have the same respective meanings given in FormulaI.

In a second particular embodiment within the ambit of the composition ofmatter aspect are the novel 1-(2-R⁴ -4-N-R⁵ -N-R⁶ -aminophenyl)-1-(1-R¹³-2-R¹⁴ -5/6-R¹⁵ -indol-3-yl)-3-(2-R² -4-N-R-N-R¹ -aminophenyl)-3-(4-R³-phenylsulfonyl)prop-1-enes of Formula I wherein A is (2-R⁴ -4-N-R⁵-N-R⁶ -aminophenyl) and B is (1-R¹³ -2-R¹⁴ -5/6-R¹⁵ -indol-3-yl) havingthe formula ##STR7## in which R, R¹, R², R³, R⁴, R⁵, R⁶, R¹³, R¹⁴, andR¹⁵ have the same respective meanings given in Formula I.

In a third particular embodiment within the ambit of the composition ofmatter aspect are the novel 1-(1-R⁷ -2-R⁸ -5/6-R⁹ -indol-3-yl)-1-(1-R¹³-2-R¹⁴ -5/6-R¹⁵ -indol-3-yl)-3-(2-R² -4-N-R-N-R¹ -aminophenyl)-3-(4-R³-phenylsulfonyl)prop-1-enes of Formula I wherein A is (1-R⁷ -2-R⁸-5/6-R⁹ -indol-3-yl) and B is (1-R¹³ -2-R¹⁴ -5/6-R¹⁵ -indol-3-yl) havingthe formula ##STR8## in which R, R¹, R², R³, R⁷, R⁸, R⁹, R¹³, R¹⁴, andR¹⁵ have the same respective meanings given in Formula I.

In its process aspect, the invention sought to be patented resides inthe process for preparing a 1-A-1-B-3-(2-R² -4-N-R-N-R¹-aminophenyl)-3-(4-R³ -phenylsulfonyl)prop-1-ene according to Formula Iwhich comprises interacting the corresponding 1-A-1-B-ethene with theappropriate 2-R² -4-N-R-N-R¹ -aminobenzaldehyde and the appropriate 4-R³-benzene sulfinic acid in the presence of an acidic catalyst in which A,B, R, R¹, R², and R³ have the same respective meanings given in FormulaI.

In one of its article of manufacture aspects, the invention sought to bepatented resides in a substrate for use in transfer imaging comprising asupport sheet coated with a layer containing as a color-formingsubstance a 1-A-1-B-3-(2-R² -4-N-R-N-R¹ -aminophenyl)-3-(4-R³-phenylsulfonyl)prop-1-ene according to Formula I wherein A, B, R, R¹,R², and R³ have the same respective meanings given in Formula I.

In a particular embodiment in accordance with its first article ofmanufacture aspect, the invention sought to be patented resides in asubstrate for use in transfer imaging comprising a support sheet coatedwith a layer containing as a color-forming substance a 1-(2-R⁴ -4-N-R⁵-N-R⁶ -aminophenyl)-1-(2-R¹⁰ -N-R¹¹ -N-R¹² -aminophenyl)-3-(2-R²-4-N-R-N-R¹ -aminophenyl)-3-(4-R³ -phenylsulfonyl)prop-1-ene accordingto Formula II wherein R, R¹, R², R³, R⁴, R⁵, R⁶, R¹⁰, R¹¹, and R¹² havethe same respective meanings given in Formula II.

In a second particular embodiment in accordance with its first articleof manufacture aspect, the invention sought to be patented resides in asubstrate for use in transfer imaging comprising a support sheet coatedwith a layer containing as a color-forming substance a 1-(2-R⁴ -4-N-R⁵-N-R⁶ -aminophenyl)-1-(1-R¹³ -2-R¹⁴ -5/6-R¹⁵ -indol-3-yl)-3-(2-R²-4-N-R-N-R¹ -aminophenyl)-3-(4-R³ -phenylsulfonyl)prop-1-ene accordingto Formula III wherein R, R¹, R², R³, R⁴, R⁵, R⁶, R¹³, R¹⁴, and R¹⁵ eachhave the same respective meanings given in Formula III.

In a third particular embodiment in accordance with its first article ofmanufacture aspect, the invention sought to be patented resides in asubstrate for use in transfer imaging comprising a support sheet coatedwith a layer containing as a color-forming substance a 1-(1-R⁷ -2-R⁸-5/6-R⁹ -indol-3-yl)-1-(1-R¹³ -2-R¹⁴ -5/6-R¹⁵ -indol-3-yl)-3-(2-R²-4-N-R-N-R¹ -aminophenyl)-3-(4-R³ -phenylsulfonyl)prop-1-ene accordingto Formula IV wherein R, R¹, R², R³, R⁷, R⁸, R⁹, R¹³, R¹⁴, and R¹⁵ eachhave the same respective meanings given in Formula IV.

In a second of its article of manufacture aspects, the invention soughtto be patented resides in a substrate for use in a pressure-sensitive orthermal-responsive marking system comprising a support sheet coated witha layer containing as a color-forming substance a 1-A-1-B-3-(2-R²-4-N-R-N-R¹ -aminophenyl)-3-(4-R³ -phenylsulfonyl)prop1-ene according toFormula I wherein A, B, R, R¹, R², and R³ have the same respectivemeanings given in Formula I.

In a particular embodiment in accordance with its second article ofmanufacture aspects, the invention sought to be patented resides in asubstrate for use in a pressure-sensitive or a thermal-responsivemarking system comprising a support sheet coated with a layer containingas a color-forming substance a 1-(2-R⁴ -4-N-R⁵ -N-R⁶-aminophenyl)-1-(2-R¹⁰ -4-N-R¹¹ -N-R¹² -aminophenyl)-3-(2-R² -4-N-R-N-R¹-aminophenyl)-3-(4-R³ -phenylsulfonyl)prop-1-ene according to Formula IIwherein R, R¹, R², R³, R⁴, R⁵, R⁶, R¹⁰, R¹¹, and R¹² have the samerespective meanings given in Formula II.

In a second particular embodiment in accordance with its second articleof manufacture aspects, the invention sought to be patented resides in asubstrate for use in a pressure-sensitive or a thermal-responsivemarking system comprising a support sheet coated with a layer containingas a color-forming substance a 1-(2-R⁴ -4-N-R⁵ -N-R⁶-aminophenyl)-1-(1-R¹³ -2-R¹⁴ -5/6-R¹⁶ -indol-3-yl)-3-(2-R² -4-N-R-N-R¹-aminophenyl)-3-(4-R³ -phenylsulfonyl)prop-1-ene according to FormulaIII wherein R, R¹, R², R³, R⁴, R⁵, R⁶, R¹³, R¹⁴, and R¹⁵ have the samerespective meanings given in Formula III.

In a third particular embodiment in accordance with its second articleof manufacture aspects, the invention sought to be patented resides in asubstrate for use in a pressure-sensitive or a thermal-responsivemarking system comprising a support sheet coated with a layer containingas a color-forming substance a 1-(1-R⁷ -2-R⁸ -5/6-R⁹ -indol-3-yl)-1-R¹³-2-R¹⁴ -5/6-R¹⁵ -indol-3-yl)-3-(2-R² -4-N-R-N-R¹ -aminophenyl)-3-(4-R³-phenylsulfonyl)prop-1-ene according to Formula IV wherein R, R¹, R²,R³, R⁷, R⁸, R⁹, R¹³, R¹⁴, and R¹⁵ have the same respective meaningsgiven in Formula IV.

In a fourth particular embodiment in accordance with its second articleof manufacture aspects, the invention sought to be patented resides in apressure-sensitive transfer sheet, adapted for use with a receivingsheet having an electron-accepting layer, comprising a support sheetcoated on one side with a layer of pressure-rupturable microcapsules,said microcapsules containing a liquid solution of a color-formingsubstance comprising at least one compound having Formula I.

In a fifth particular embodiment in accordance with its second articleof manufacture aspects, the invention sought to be patented resides in athermal-responsive record material comprising a supprt sheet coated onone side with a layer containing a mixture comprising at least onecolor-forming compound having Formula I and an acidic developer arrangedsuch that application of heat will produce a mark-forming reactionbetween the color-forming compound and the acidic developer.

As used herein the terms "non-tertiary C₁ to C₄ alkyl", "non-tertiary C₁to C₈ alkyl" and "non-tertiary C₁ to C₁₆ alkyl" denote saturatedmonovalent straight or branched aliphatic hydrocarbon radicals includingmethyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, 1-methylbutyl,3-methylbutyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl,n-doceyl, and the like.

The term "non-tertiary C₁ to C₄ alkoxy" includes saturated acyclic,straight or branched-chain groups such as methoxy, ethoxy, propoxy,isopropoxy, butoxy, sec-butoxy and isobutoxy.

As used herein the terms "halo" and "halogen" include chloro, fluoro,bromo, and iodo. Chloro is the preferred halo substituent because of therelatively low cost and ease of preparation of the requiredchloro-substituted intermediates and because the other halogens offer noparticular advantages over chloro. However, the other above-named halosubstituents are also satisfactory.

The compounds of Formula I hereinabove are essentially colorless in thedepicted form. When contacted with a color developer such as thoseconventionally employed in carbonless duplicating systems which aregenerally acidic in nature, the compounds of Formula I develop purple,blue, and cyan-colored images. Illustrative of specific examples ofthese color developers are clay minerals such as acid clay, active clay,attapulgite, and silton clay; organic acids such as tannic acid, gallicacid, propyl gallate, and so forth; acid polymers such asphenol-formaldehyde resins, phenol acetylene condensation resins,condensates between an organic carboxylic acid having at least onehydroxy group and formaldehyde, and so forth; metal salts or aromaticcarboxylic acids such as zinc salicylate, tin salicylate, zinc 2-hydroxynaphthoate, zinc 3,5-di-tertiary-butyl salicylate, oil soluble metalsalts of phenol-formaldehyde novolak resins, and so forth. These colordevelopers are also useful in transfer imaging systems. The developedimages are very insensitive to light, are of good tinctorial strength,possess excellent xerographic copiability and enhanced solubility incommon organic solvents. The compounds are thus highly suitable for useas colorless precursors, that is, color-forming substances inpressure-sensitive carbonless duplicating systems. The compounds ofFormula I can be used alone as color formers to produce images which arereadily copiable, or can be used as toners to admixture with other colorformers to produce images of neutral shade which desirably are readilycopiable by xerographic means.

The compounds of Formula I may be incorporated into transfer imagingsystems which refer to office based systems suitable for makingphotocopies. One such system is disclosed in U.S. Pat. No. 4,399,209. Inthis system, the color-forming phthalides of Formula I aremicroencapsulated together with a photo-initiator in a photo-sensitivecomposition in pressure-rupturable capsules. The microcapsules are thencoated onto a surface of a substrate. Images are formed by image-wiseexposing the encapsulated bearing substrate to actinic radiation andrupturing the capsules in the presence of a developer to obtain animage.

The compounds of this invention may be incorporated in any of thecommercially accepted systems known in the carbonless duplicating art. Atypical technique for such applications is as follows. Solutionscontaining one or more colorless compounds of Formula I optionally inadmixture with other color formers, in suitable solvents, aremicroencapsulated by well known procedures, for example, as described inU.S. Pat. Nos. 3,369,649; 3,429,827; and 4,000,087. The microcapsulesare coated on the reverse side of a sheet with the aid of a suitablebinder and the coated transfer sheet is then assembled in a manifoldwith the microcapsule coated side in contact with a receiving sheetcoated with an electron-accepting substance, for example, silton clay ora phenolic resin. Application of pressure to the manifold, such as thatexerted by a stylus, typewriter, or other form of writing or printing,causes the capsules on the reverse side to rupture. The solution of thecolor formers released from the ruptured microcapsules flows to thereceiving sheet and, on contact with the acidic medium thereon, formspurple, blue, and cyan-colored images of good tinctorial strength. Itis, of course, obvious that variants of this mode of application can beutilized. For example, the receiving sheet in a manifold canalternatively be coated with the subject compounds and the acidicdeveloping agent can be contained in microcapsules applied to thereverse side of the top sheet in the manifold, or the receiving sheetcan be coated with a mixture containing both the acidic developing agentand the microencapsulated color former.

It has also been found that when the compounds of Formula I areintimately mixed with an acidic developer, for example, Bisphenol A ofthe type generally employed in thermal papers such as described in U.S.Pat. No. 3,539,375, that is, papers which produce a colored image whencontacted with a heated stylus or heated type, heating of said mixtureproduces a colored image of varying shades from purple to cyan dependingon the particular compound of the invention employed. The ability of thecompounds of Formula I to form a deep color when heated in admixturewith an acidic developer such as Bisphenol A, makes them useful inthermal paper marking systems, either where an original or a duplicatecopy is prepared by contacting the thermal paper with a heated stylus orheated type in any of the methods generally known in the art.

The compounds of Formula I, having an ethenyl linkage, have beein foundto exhibit light absorption in their colored form at wavelengths nearerto the infrared then do similar compounds without the ethenyl moieties.It is an object of this invention to provide compounds possessing bothnear infrared color response and chromogenic properties when thecompounds are incorporated into a pressure-sensitive orthermal-responsive carbonless duplicating system and transfer imagingsystem involving reactive contact with a color-activating material todevelop dark colored images in areas where the marking is desired. Thedeveloped colored images of the compounds of Formula I absorbing at ornear the infrared wavelengths especially relate to providing a colorwhich is particularly visible to machine readers and copiers, such asthe optical character reading machines. The various optical character ormark reading machines are used for reading the record images developedon a recording material. Generally the developed images on theconventional recording materials are those which can be read by theoptical reading machines which are capable of reading for the visiblewavelength range of 500 nm to 880 nm. One example of record materialwhich is used and in which the compounds of Formula I find use incarbonless duplicating systems and image transfer systems is the use ofbusiness forms.

The best mode contemplated by the inventors of carrying out thisinvention will now be described so as to enable any person skilled inthe art to which it pertains to make and use the same.

In accordance with the aforementioned process aspect of this invention,the compounds of Formula I are obtained by reacting one molecularproportion of a 1-A-1-B-ethene with one molecular proportion of a 2-R²-4-N-R-N-R¹ -benzaldehyde and one molecular proportion of a 4-R³-benzenesulfinic acid which is conveniently added to the reaction as analkali metal salt such as the sodium salt. The reaction is convenientlycarried out in an aliphatic alcohol, for example, ethanol or propanol inthe approximate temperature range of from 60° C. to the refluxtemperature of the reaction mixture from approximately three hours toapproximately forty-eight hours. The propenes of Formula I thus obtainedcan be isolated by several methods. One such method of isolation is topour the reaction mixture into ice water and to filter the propenes fromthe mixture. An alternative method of isolation is to pour the reactionmixture into a mixture of water immiscible organic liquid in which thepropenes are soluble, such as toluene and ice water. The organic liquidlayer containing the propenes is separated from the aqueous layer andthe propene is isolated by removing the organic liquid by evaporation ordistillation. The propene, once isolated, can be purified byconventional means such as trituration or recrystallization from asuitable solvent and then collected by filtration. Purification can alsobe effected by column chromatography. The propene to be purified isdissolved in a suitable organic liquid or combination of organic liquidsand the solution is passed through a chromatography column which hasbeen packed with a suitable substrate, for example, silica gel,cellulose, alumina, and the like. Numerous fractions are collected andanalyzed to determine fraction(s) containing the desired propene. Thefraction(s) which contain the desired product are then combined (if morethan one) and concentrated to obtain the propene which is then collectedby filtration.

The requisite 1-A-1-B-ethenes required in the practice of this inventionare the subject of a separate patent application. The 1-A-1-B-etheneswherein A is a 1-R⁷ -2-R⁸ -5/6-R⁹ -indol-3-yl and B is a 1-R¹³ -2-R¹⁴-5/6-R¹⁵ -indol-3-yl are conveniently prepared by interacting onemolecular proportion of a 1-R⁷ -2-R⁸ -5/6-R⁹ -indole and one molecularproportion of a 1-R¹³ -2-R¹⁴ -5/6-R¹⁵ -indole with one molecularproportion of acetic anhydride. The reaction is conveniently carried outin excess acetic anhydride at a temperature in the range of roomtemperature to 90° C. for from approximately two hours to approximatelytwenty hours in the presence of an acidic catalyst, such asmethanesulfonic acid. The product thus obtained can be isolated bypouring the reaction mixture into an aqueous base, such as ammoniumhydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, orsodium bicarbonate, and the product extracted with a water-immiscibleorganic liquid, such as toluene, xylene, or chlorobenzene, followed byevaporation of the organic liquid leaving the product as a residue. Theproduct, once isolated, can be purified by conventional means, such astrituration or recrystallization, from a suitable organic liquid or by avacuum distillation. Alternatively, the product thus obtained can beisolated by pouring an organic liquid such as isopropyl alcohol into thereaction mixture and filtering the desired product.

The 1-A1-B-ethenes wherein A is 2-R⁴ -4-N-R⁵ -N-R⁶ -aminophenyl and B is1-R¹³ -2-R¹⁴ -5/6-R¹⁵ -indol-3-yl are conveniently prepared byinteracting one molecular proportion of a 1-R¹³ -2-R¹⁴ -5/6-R¹⁵ -indolewith one molecular proportion of the appropriate 2-R⁴ -4-N-R⁵ -N-R⁶-aminoacetophenone. The reaction is conveniently carried out in anorganic liquid, such as ethyl alcohol, 2-ethoxyethyl alcohol, isopropylalcohol, and the like, in the presence of an acidic catalyst, such asmethanesulfonic acid, hydrochloric acid, hydrobromic acid, or aceticacid, at a temperature in the range of room temperature to the refluxtemperature of the organic liquid for from approximately eight hours toapproximately thirty hours. The product thus obtained can be isolatedand purified, if needed, in a manner identical to the process aspectdiscussed directly above.

Throughout this application where the possibility of different isomericproducts exist, the nomenclature "5/6" is adopted meaning the productobtained or claimed is either a mixture of isomers or one of the twoisomers.

The indoles represented by the formulas 1-R⁷ -2-R⁸ -5/6-R⁹ -indole and1-R¹³ -2-R¹⁴ -5/6-R¹⁵ -indole in which 5/6 refers to a substituent inthe 5 and/or 6-position of the benzene ring of the indole and, which arerequired for the interaction with acetic anhydride and the acetophenonesto obtain the propenes of Formula I form an old and well known class ofcompounds readily obtained by conventional procedures well known in theart. The following list of compounds exemplifies indoles which areuseful in the practice of the step in the processes of this inventionfor producing the aforesaid propenes of Formula I. Indole,1-methylindole, 2-methyl-indole, 1,2-dimethylindole,1-ethyl-2-methylindole, 2-phenylindole, 1-propyl-2-methylindole,1-benzyl-2-methylindole, 1-butyl-2-methylindole, 1-octyl-2-methylindole,2-ethyl-5-methylindole, 1-benzyl-5-fluoroindole, 1-methyl-6-nitroindole,5-methoxy-1-butylindole, 1-allyl-2-methylindole,1,2-dimethyl-6-nitroindole, 1-(4 -chlorobenzyl)-2-methyl-5-nitroindole,2-ethylindole, 2-ethyl-1-methylindole, 1-isopropylindole,2-isopropylindole, 1-methyl-5-bromo-6-nitroindole,2,5,6-trimethylindole, 1-isobutyl-2-methylindole,6-bromo-2-methylindole, 1-hexylindole,1-(2,5-dimethylbenzyl)-2-methylindole, 2-propylindole,6-chloro-2-phenylindole, 1-(2-ethylhexyl)-2-methylindole,1-(2,6-dichlorobenzyl)-2-methylindole, 1-vinyl-2-methylindole,2-ethyl-6-methylindole, 6-fluoro-1-benzylindole,1-(4-bromobenzyl)-2-isopropylindole, 1-(3-chlorobenzyl)-2-ethylindole,5-chloro-1-benzylindole, 1-(2-fluorobenzyl)-2-methylindole,5-iodo-1-(1-methylhexyl)indole, 5,6-dimethoxyindole,1-(2-methylbenzyl)-2-methylindole, 5,6-dichloro-2-phenylindole,1-isoamylindole, 1-[3-(2-methyl)-1-propenyl]-2-methylindole,1-methoxyethyl-2-methylindole, 1-dodecyl-2-methylindole,1-tetradecyl-2-methylindole, 1-hexadecyl-2-methylindole,1-decyl-2-phenylindole, 1-heptyl-2-ethylindole, 1-nonyl-2-propylindole,and 1-phenoxyethyl-2-methylindole.

The molecular structures of the compounds were assigned on the basis ofthe modes of synthesis and a study of their infrared and nuclearmagnetic resonance spectra.

The following examples will further illustrate the invention without,however, limiting it thereto.

EXAMPLE 1

A mixture of 9.0 g of 4-N,N-dimethylaminobenzaldehyde, 16.2 g of1,1-bis(4-N,N-dimethylaminophenyl)ethene, 15.0 g of sodiummethylbenzenesulfinate monohydrate, 225.0 ml of 3A ethanol, and 18.0 mlof concentrated hydrochloric acid was maintained at reflux temperaturefor approximately sixteen hours. The mixture was cooled to roomtemperature and poured into an agitated mixture of 750.0 ml of tolueneand 1,000 ml of water. The toluene layer was separated and washed withwater, then with saturated sodium chloride solution and separated. Thetoluene was evaporated under vacuum to leave a residue which wascrystallized from a mixture of isopropanol and hexane to give 6.64 g of1,1-bis(4-N,N-dimethylaminophenyl)-3-(4-N,N-dimethylaminophenyl)-3-(4-methylbenzenesulfonyl)propene(Formula II: R, R¹, R³, R⁵, R⁶ ═CH₃ ; R², R⁴, R¹⁰ ═H; Z═N(CH₃)₂), a palegreen solid with a melting point of 210° to 213° C. Significantidentifying infrared absorption maxima occurred at 1886 cm⁻¹, 1750 cm⁻¹,1600 cm⁻¹, 1150 cm⁻¹, and 820 cm⁻¹. Nuclear magnetic resonance wasconsistent with the assigned structure. When spotted from an acetonesolution onto phenolic resin, acid clay, or organic and coated papers,blue-colored images were produced. An acetone solution of the productand Bisphenol A was coated onto a glass plate and allowed to dry. Thetransmission spectrum of the coating had significant adsorption at 730and 775 nanometers.

EXAMPLE 2

In a manner similar to that given in Example 1, 3.3 g of4-N,N-diethylaminobenzaldehyde was reacted with 5.4 g of1,1-bis(4-N,N-dimethylaminophenyl)ethene, 5.0 g of sodium4-methylbenzenesulfinate monohydrate in 75.0 ml of 3A ethanol and 6.0 mlconcentrated hydrochloric acid for approximately 8.5 hours at refluxtemperature. There was obtained, 2.4 g of1,1-bis(4-N,N-dimethylaminophenyl)-3-(4-N,N-diethylaminophenyl)-3-(4-methylbenzenesulfonyl)prop-1-ene.(Formula II: R, R¹ ═C₂ H₅ ; R², R⁴, R¹⁰ ═H; R³, R⁵, R⁶ ; Z═N(CH₃)₂, apale blue solid which melted at 174° to 177° C. Identifying infraredabsorption maxima appeared at 1875 cm⁻¹ (weak), 1610 cm⁻¹, 1150 cm⁻¹,and 820 cm⁻¹. This product formed cyan-colored images when spotted froman acetone solution onto phenolic resin, acid clay, or organic acidcoated papers. An acetone solution of the product and Bisphenol A wascoated onto a glass plate and dried. The transmission spectrum of thecoating had significant adsorptions at 727 and 762 nanometers.

EXAMPLE 3

Following the procedure described in Example 1, 3.0 g of4-N,N-dimethylaminobenzaldehyde, 5.4 g of1,1-bis(4-N,N-diethylaminophenyl)ethene, 5.0 g of sodium4-methylbenzenesulfinate monohydrate, 75.0 ml of 3A ethanol, and 6.0 mlof concentrated hydrochloric acid were interacted for approximatelynineteen and one-half hours at reflux temperature to obtain 0.87 g of1,1-bis(4-N,N-diethylaminophenyl)-3-(4-N,N-dimethylaminophenyl)-3-(4-methylbenzenesulfonyl)prop-1-ene(Formula II: R, R¹, R³ ═CH₃ ; R², R⁴, R¹⁰ ═H; R⁵, R⁶ C₂ H₅ ; Z═N(C₂ H₅)₂a pale green solid which melted at 182° to 184° C. with identifyinginfrared absorption maxima at 1610 cm⁻¹, 1150 cm⁻¹, and 820 cm⁻¹. Whenspotted from acetone solution onto phenolic resin, acid clay, or organicacid coated paper, turquoise-colored images were produced. An acetonesolution of the product and Bisphenol A was coated onto a glass plateand dried. The transmission spectrum of the coating had significantadsorptions at 725 and 750 nanometers.

EXAMPLE 4

Proceeding in a manner similar to that described in Example 1 above, 3.0g of 4-dimethylaminobenzaldehyde, 5.3 g of1,1-bis(4-dimethylaminophenyl)ethene, and 5.0 g of sodium4-methylbenzenesulfinate monohydrate was interacted in a mixture of100.0 ml of ethanol and 7.0 ml of concentrated hydrochloric acid toobtain 5.59 g of1,1-3-tris(4-dimethylaminophenyl)-3-(4-methylphenylsulfonyl)prop-1-ene(Formula II: R, R¹, R², R³, R⁵, R⁶ ═CH₃ ; R⁴, R¹⁰ ═HZ═N(CH₃)₂), a palegreen solid which melted at 180.5° to 184.5° C. Significant infraredmaxima appeared at 1615 cm⁻¹, 1356 cm⁻¹, and 823 cm⁻¹. An acetonesolution of the product spotted onto a phenolic resin, acidic clay, andan organic acid coated paper developed a blue-colored image.

EXAMPLE 5

With stirring, a mixture of 2.91 g of1,1-bis(4-N,N-dimethylaminophenyl)ethene, 2.16 g of2-methyl-4-N,N-diethylaminobenzaldehyde, 2.70 g of sodium4-methylbenzenesulfinate monohydrate in 34.0 ml of 3A ethanol and 5.0 mlof concentrated hydrochloric acid was maintained at reflux temperaturefor approximately nine hours. The reaction mass was poured onto anagitated mixture of 1,000 ml of water and 750.0 ml of toluene. Thetoluene layer was separated, washed with water, and saturated saltsolution. The separated toluene layer was evaporated and the residuemixture was column chromatographed on silica gel using a toluene ethylacetate, 3:1, eluents. The desired fractions were evaporated to drynessand recrystallized from a mixture of hexane and isopropanol to obtain0.76 g of1,1-bis(4-N,N-dimethylaminophenyl)-3-(2-methyl-4-N,N-diethylaminophenyl)-3-(4-methylbenzenesulfonyl)prop-1-ene(Formula II: R, R¹ ═C₂ H₅ ; R², R³, R⁵, R⁶ ═CH₃ ; R⁴, R¹⁰ ═H; Z═N(CH₃)₂,an off-white-colored solid which melted at 176° to 180° C. Identifyinginfrared absorption maxima appeared at 1610 cm⁻¹, 1290 cm⁻¹, 1150 cm⁻¹,830 cm⁻¹, and 815 cm⁻¹. When an acetone solution of the product wasspotted on a phenolic resin, acid clay, or organic acid coated paper,blue-colored images were produced. An acetone solution of the productand Bisphenol A was coated onto a glass plate and dried. Thetransmission spectrum of the coating had significant adsorptions at 735and 780 nanometers.

EXAMPLE 6

In a manner similar to the procedure described in Example 4, a mixtureof 3.0 g of 4-N,N-dimethylaminobenzaldehyde, 4.5 g of1-phenyl-1-(4-N,N-dimethylaminophenyl)ethene, 5.0 g of sodium4-methylbenzenesulfinate monohydrate were reacted in 75.0 ml of 3Aethanol and 5.0 ml of concentrated hydrochloric acid was interacted atreflux temperature for approximately nine hours to obtain 0.98 g of1-phenyl-1-(4-N,N-dimethylaminophenyl)-3-(4-N,N-dimethylaminophenyl)-3-(4-methylbenzenesulfonyl)prop-1-ene(Formula II: R, R¹, R³, R⁵, R⁶ ═CH₃ ; R², R⁴, R¹⁰, Z═H a white solidwhich melted at 168° to 170° C. Significant infrared absorption maximawere observed at 1620 cm⁻¹, 1295 cm⁻¹, 1152 cm⁻¹, 828 cm⁻¹, and 818 cm¹.An acetone solution of the product spotted on phenolic resin, acid clay,or organic acid coated paper developed weak green-colored images. Anacetone solution of the product and Bisphenol A was coated on a glassplate and dried. The transmission spectrum of the coating hadsignificant adsorption at 755 and 785 nanometers.

EXAMPLE 7

Proceeding in a manner similar to that described in Example 4 above, 3.8g of 4-(piperidin-1-yl)benzaldehyde, 5.4 g of1,1-bis(4-N,N-dimethylaminophenyl)ethene, 5.0 g of sodium4-methylbenzenesulfinate monohydrate, 100.0 ml of 3A ethanol, and 5.0 mlof concentrated hydrochloric acid were maintained at reflux temperaturefor approximately five hours to obtain 0.4 g of1,1-bis(4-N,N-dimethylaminophenyl)-3-[4-(piperidin-1-yl)phenyl]-3-(4-methylbenzenesulfonyl)prop-1-ene(Formula II: R, R¹ ═piperidinyl; R², R⁴, R¹⁰ ═H; R³, R⁵, R⁶ ; Z═NCCH₃)₂,═CH₃), a green solid melting over the range of 78° to 92° C. Significantinfrared maxima appeared at 1150 cm⁻¹ and 830 cm⁻¹. An acetone solutionof the product spotted onto phenolic resin, acid clay, or organic acidcoated paper produced deep green-colored images. An acetone solution ofthe product and Bisphenol A was coated onto a glass plate and dried. Thetransmission spectrum of the coating had significant adsorptions at 730and 760 nanometers.

EXAMPLE 8

A mixture consisting of 7.5 g of 4-N,N-dimethylaminobenzaldehyde, 17.1 gof 1,1-bis(1-ethyl-2-methylindol-3-yl)ethene, 8.9 g of sodium4-methylbenzenesulfonyl monohydrate, 100.0 ml of 3A ethanol, and 5.0 mlof hydrochloric acid were combined and maintained at reflux temperaturefor approximately sixteen hours. Reaction was incomplete at this time,so an additional 3.4 g of (1-ethyl-2-methylindol-3-yl)ethene were addedand reflux was continued for approximately six hours additional. Thereaction slurry was poured onto a mixture of 1,000 ml of toluene, 1,000ml of ice water, and 20.0 ml of ammonium hydroxide. The toluene layercontaining the product was separated, washed with saturated saltsolution and the toluene evaporated. The tarry residue waschromatographed on a column packed with silica gel using a toluene ethylacetate, 3:1, eluent. The solid obtained by this method wasrecrystallized to obtain 0.67 g of1,1-bis(1-ethyl-2-methylindol-3-yl)-3-(4-N,N-dimethylaminophenyl)-3-(4-methylbenzenesulfonyl)prop-1-ene(Formula IV: R, R¹, R³, R⁸, R¹⁴ ═CH₃ ; R², R⁹, R¹⁵ ═H; R⁷, R¹³ ═C₂ H₅),a yellow solid which melted at 198° to 200° C. Significant infraredabsorption maxima occurred at 1610 cm⁻¹, 1140 cm⁻¹, 1090 cm⁻¹, and 750cm⁻¹. An acetone solution of the product spotted on phenolic resin, acidclay, or organic acid coated paper developed blue-colored images. Anacetone solution of the product and Bisphenol A was coated onto a glassplate and dried. The transmission spectrum of the coating hadsignificant adsorption at 683 and 725 nanometers.

EXAMPLE 9

A mixture of 3.0 g of 4-N,N-diethylaminobenzaldehyde, 12.0 g of1-(4-N,N-dimethylaminophenyl)-1-(1-n-octyl-2-methylindol-3-yl)ethene,6.0 g of sodium 4-methylbenzenesulfinate monohydrate, 100.0 ml of 3Aethanol and 8.0 ml of concentrated hydrochloric acid was maintained atreflux temperature for approximately six hours. The reaction mixture wascooled and poured into a mixture of 400.0 ml of toluene, 400.0 ml of icewater, and 100.0 ml of concentrated ammonium hydroxide. The toluenelayer was separated, washed with water and saturated salt solution, thenevaporated to dryness. The oily residue was separated by columnchromatography using silica gel and eluenting first with toluene, thenwith 1:3 ethyl acetate:toluene solution to obtain 0.41 g of1-(4-N,N-dimethylaminophenyl)-1-(1-n-octyl-2-methylindol-3-yl)-3-(4-N,N-diethylaminophenyl)-3-(4-methylbenzenesulfonyl)prop-1-ene(Formula III: R, R¹ ═CH₂ H₅ ; R², R⁴, R¹⁵ ═H; R³, R⁵, R⁶, R¹⁴ ═CH₃ ; R¹³═n--C₈ H₁₇), an oil with significant infrared absorption maxima at 1610cm⁻¹, 1140 cm⁻¹, and 750 cm⁻¹. An acetone solution of the productspotted on phenolic resin, acid clay, or organic acid coated papersdeveloped blue-green to blue-black-colored images. An acetone solutionof the product and Bisphenol A was coated onto a glass plate and dried.The transmission spectrum of the coating had significant adsorption at660 and 770 nanometers.

It is contemplated that by following procedures similar to thosedescribed in Examples 1 to 7 above but employing the appropriatelysubstituted 2-R² -4-N-R-N-R¹ -aminobenzaldehyde with the appropriatelysubstituted 1-(2-R⁴ -4-N-R⁵ -N-R⁶ -aminophenyl)-1-(2-R¹⁰ -4-Z-phenyl)ethene and sodium 4-R³ -benzenesulfinate there will be obtained theappropriate 1-(2-R⁴ -4-N-R⁵ -N-R⁶ -aminophenyl)-1-(2-R¹⁰-4-Z-phenyl)-3-(2-R² -4-N-R-N-R¹ -aminophenyl)-3-(4-R³ -benzenesulfonyl)propene of Formula II, Examples 10 to 27 presented in Table 1hereinbelow.

                                      TABLE VI                                    __________________________________________________________________________    1-(2-R.sup.4 --4-N--R.sup.5 --N--R.sup.6 --Aminophenyl)-1-(2-R.sup.10         --Z--phenyl)-3-(2-R.sup.2 --4-N--R--N--R.sup.1 --aminophenyl)-                3-(4-R.sup.3 --benzenesulfonyl) of propenes of Formula II                     EX.                                                                              R          R.sup.1                                                                           R.sup.2                                                                             R.sup.3                                                                           R.sup.4                                                                            R.sup.5   R.sup.6                                                                           R.sup.10                                                                           Z                         __________________________________________________________________________    10 C.sub.4 H.sub.9                                                                          C.sub.4 H.sub.9                                                                   CH.sub.3 O                                                                         C.sub.12 H.sub.25                                                                  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                    N(C.sub.2 H.sub.5).sub                                                        .2                        11 C.sub.8 H.sub.17                                                                         C.sub.8 H.sub.17                                                                  CH.sub.3                                                                           Cl   C.sub.2 H.sub.5                                                                    C.sub.6 H.sub.5 CH.sub.2                                                                C.sub.2 H.sub.5                                                                   CH.sub.3                                                                           N(C.sub.4 H.sub.9).sub                                                        .2                        12 C.sub.6 H.sub.5 CH.sub.2                                                                 C.sub.2 H.sub.5                                                                   Cl   NO.sub.2                                                                           CH.sub.3 O                                                                         4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2                                                     H   CH.sub.3 O                                                                         N(C.sub.                                                                      6 H.sub.5)(CH.sub.3)      13 C.sub.6 H.sub.13                                                                         C.sub.6 H.sub.13                                                                  F    C.sub.8 H.sub.17                                                                   C.sub.4 H.sub.9 O                                                                  CH.sub.3  CH.sub.3                                                                          Cl   N(C.sub.2 H.sub.5)(C.s                                                        ub.6 H.sub.5 CH.sub.2)                                                        .                         14 4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2                                                      H   NO.sub.2                                                                           C.sub.2 H.sub.5                                                                    C.sub.8 H.sub.17                                                                   C.sub.6 H.sub.5                                                                         C.sub.2 H.sub.5                                                                   Br   N(C.sub.8 H.sub.17).su                                                        b.2                       15 4-ClC.sub.6 H.sub.4 CH.sub.2                                                             CH.sub.3                                                                          C.sub.2 H.sub.5                                                                    C.sub.4 H.sub.9                                                                    F    C.sub.4 H.sub.9                                                                         C.sub.4 H.sub.9                                                                   NO.sub.2                                                                           N(C.sub.6 H.sub.5                                                             CH.sub.2).sub.2           16 4-CH.sub.3 OC.sub.6 H.sub.4 CH.sub.2                                                     C.sub.3 H.sub.7                                                                   C.sub.4 H.sub.9                                                                    H    C.sub.2 H.sub.5 O                                                                  C.sub.8 H.sub.17                                                                        C.sub.8 H.sub.17                                                                  C.sub.4 H.sub.9 O                                                                  H                         17 C.sub.12 H.sub.25                                                                        C.sub.12 H.sub.25                                                                 C.sub.8 H.sub.17 O                                                                 C.sub.2 H.sub.5                                                                    Cl   4-ClC.sub.6 H.sub.4 CH.sub.2                                                            H   C.sub.12 H.sub.25                                                                  H                         18 C.sub.16 H.sub.33                                                                        C.sub.16 H.sub.33                                                                 CH.sub.3                                                                           C.sub.12 H.sub.25                                                                  C.sub.8 H.sub. 17 O                                                                3-NO.sub.2 C.sub.6 H.sub.4 CH.sub.2                                                     CH.sub.3                                                                          C.sub.8 H.sub.17 O                                                                 N(C.sub.2 H.sub.5)        19 C.sub.6 H.sub.5 CH.sub.2                                                                 C.sub.4 H.sub.9                                                                   Br   Br   C.sub.12 H.sub.25                                                                  C.sub.4 H.sub.9                                                                         C.sub.4 H.sub.9                                                                   Br   N(CH.sub.3)(CH.sub.3                                                          C.sub.6 H.sub.4)          20 2,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2                                            H   Cl   C.sub.3 H.sub.7                                                                    C.sub.4 H.sub.9                                                                    C.sub.16 H.sub.33                                                                       H   C.sub.4 H.sub.9                                                                    H                         21 C.sub.6 H.sub.5                                                                          C.sub.2 H.sub.5                                                                   NO.sub.2                                                                           C.sub.4 H.sub.9                                                                    Cl   C.sub.6 H.sub.5 CH.sub.2                                                                C.sub.2 H.sub.5                                                                   C.sub.8 H.sub.17                                                                   N(CH.sub.3).sub.2         22 4-CH.sub.3 C.sub.6 H.sub.5                                                               CH.sub.3                                                                          C.sub.4 H.sub.9 O                                                                  Cl   C.sub.2 H.sub.5                                                                    C.sub.16 H.sub.33                                                                       C.sub.16 H.sub.33                                                                 F    N(C.sub.2 H.sub.5).sub                                                        .2                        23 4-CH.sub.3 OC.sub.6 H.sub.4                                                              C.sub.2 H.sub.5                                                                   C.sub.3 H.sub.7                                                                    C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           2,4(CH.sub.3).sub.2 C.sub.3 H.sub.2                                                     HH  C.sub.16 H.sub.33                                                                  H                         24 3-NO.sub.2 C.sub.6 H.sub.4 CH.sub. 2                                                     H   CH.sub.3                                                                           C.sub.4 H.sub.9                                                                    Br   C.sub.4 H.sub.9                                                                         C.sub.4 H.sub.9                                                                   C.sub.2 H.sub.5                                                                    N(CH.sub.3)(C.sub.6                                                           H.sub.5)                  25 C.sub.14 H.sub.29                                                                        C.sub.14 H.sub.29                                                                 C.sub.6 H.sub.13 O                                                                 F    C.sub.8 H.sub.17                                                                   4-CH.sub.3 OC.sub.6 H.sub.4 CH.sub.2                                                    C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5 O                                                                  NHC.sub.6 H.sub.5         26 C.sub.4 H.sub.9                                                                          C.sub.2 H.sub.5                                                                   C.sub.12 H.sub.25                                                                  Br   C.sub.4 H.sub.9 O                                                                  C.sub.6 H.sub.5                                                                         CH.sub.3                                                                          CH.sub.3                                                                           H                         27 3-NO.sub.2 C.sub.6 H.sub.4                                                               CH.sub.3                                                                          C.sub.4 H.sub.9                                                                    C.sub.12 H.sub.25                                                                  NO.sub.2                                                                           4-CH.sub.3 C.sub.6 H.sub.5                                                              C.sub.2 H.sub.5                                                                   NO.sub.2                                                                           N(C.sub.16 H.sub.33).s                                                        ub.2                      __________________________________________________________________________

It is contemplated that by following procedure similar to that describedin Example 9 above but employing the appropriately substituted 2-R²-4-N-R-N-R¹ -aminobenzaldehyde with the appropriately 1-(2-R⁴ -N-R⁵-N-R⁶ -aminophenyl)-1-(1-R¹³ -2-R¹⁴ -5/6-R¹⁵ -indol-3-yl)ethene andsodium 4-R³ -benzenesulfinate there will be obtained the appropriate1-(2-R⁴ -4-N-R⁵ -N-R⁶ -aminophenyl)-1-(1-R¹³ -2-R¹⁴ -5/6-R¹⁵-indol-3-yl)-3-(2-R³ -benzenesulfonyl) propene of Formula III, Examples28 to 45 present in Table II hereinbelow.

    TABLE II      1-(2-R.sup.4 --4-N--R.sup.5 --N--R.sup.6 --Aminophenyl)-1-(1-R.sup.13     --2-R.sup.14 --5/6-R.sup.15 --indol-3-yl)-3- (2-R.sup.2      --4-N--R--N--R.sup.1 --aminophenyl)-3-(4-R.sup.3      --benzenesulfonyl)propene of Formula III EX. R R.sup.1 R.sup.2 R.sup.3     R.sup.4 R.sup.5 R.sup.6 R.sup.13 R.sup.14 R.sup.15       28 3-NO.sub.2 C.sub.6 H.sub.4 CH.sub.3 CH.sub.3 O C.sub.12 H.sub.25     NO.sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.6 H.sub.5 OC.sub.2     H.sub.4 H 5-CH.sub.3 29 C.sub.4 H.sub.9 C.sub.2 H.sub.5 CH.sub.3 Cl     C.sub.4 H.sub.9 O C.sub.6 H.sub.5 CH.sub.2 C.sub.2 H.sub.5 C.sub.8     H.sub.17 C.sub.2 H.sub.5 5-F 30 C.sub.14 H.sub.29 C.sub.14 H.sub.29 Cl     NO.sub.2 C.sub.8 H.sub.17 4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2 H C.sub.4     H.sub.9 C.sub.3 H.sub.7 6-NO.sub.2 31 3-NO.sub.2 C.sub.6 H.sub.4     CH.sub.2 H F C.sub.8 H.sub.17 Br CH.sub.3 CH.sub.3 C.sub.10 H.sub.33     CH.sub.3 5-CH.sub.3 O 32 4-CH.sub.3 OC.sub.6 H.sub.4 C.sub.2 H.sub.5     NO.sub.2 C.sub.2 H.sub.5 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5     C.sub.2 H.sub.5 OC.sub.2 H.sub.4 H 6-NO.sub.2 33 4-CH.sub.3 C.sub.6     H.sub.5 CH.sub.3 C.sub.2 H.sub.5 C.sub.4 H.sub.9 C.sub.2 H.sub.5 C.sub.4     H.sub.9 C.sub.4 H.sub.9 C.sub.6 H.sub.4 CH.sub.2 C.sub.4 H.sub.9 H 34     C.sub.6 H.sub.5 C.sub.2 H.sub.5 C.sub.4 H.sub.9 H Cl C.sub.8 H.sub.17     C.sub.8 H.sub.17 4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.5     5-NO.sub.2 35 2,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2 H C.sub.8     H.sub.17 O C.sub.2 H.sub.5 C.sub.4 H.sub.9 4-ClC.sub.6 H.sub.4 CH.sub.2     H C.sub.12 H.sub.25 C.sub.2 H.sub.5 5-Br--6-NO.sub.2 36 C.sub.6 H.sub.5     CH.sub.2 C.sub.4 H.sub.9 CH.sub. 3 C.sub.12 H.sub.25 C.sub.12 H.sub.25     3-NO.sub.2 C.sub.6 H.sub.4 CH.sub.2 CH.sub.3 C.sub.9 H.sub.19 C.sub.4     H.sub.9 5,6-(CH.sub.3).sub.2 37 C.sub.16 H.sub.33 C.sub.16 H.sub.33 Br     Br C.sub.8 H.sub.17 O C.sub.4 H.sub.9 C.sub.4 H.sub.9 4-CH.sub.3     OC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.5 6-Br 38 C.sub.12 H.sub.25     C.sub.12 H.sub.25 Cl C.sub.3 H.sub.7 Cl C.sub.16 H.sub.33 H C.sub.14     H.sub.29 H 6-Cl 39 4-CH.sub.3 OC.sub.6 H.sub.4 CH.sub.2 C.sub.3 H.sub.7     NO.sub.2 C.sub.4 H.sub.9 C.sub.2 H.sub.5 O C.sub.6 H.sub.5 CH.sub.2     C.sub.2 H.sub.5 4-ClC.sub.6 H.sub.4 CH.sub.2 C.sub.3 H.sub.7 5-CH.sub.3     40 4-ClC.sub.6 H.sub.4 CH.sub.2 CH.sub.3 C.sub.4 H.sub.9 O Cl F C.sub.16     H.sub.33 C.sub.16 H.sub.33 C.sub.5 H.sub.11 C.sub.4 H.sub.9 6-Cl 41     4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2 H C.sub.3 H.sub.7 C.sub.2 H.sub.5     C.sub.8 H.sub.17 2,4-(CH.sub. 3).sub.2 C.sub.6 H.sub.3 CH.sub.2 H     C.sub.8 H.sub.17 C.sub.2 H.sub.5 6-CH.sub.3 42 C.sub.6 H.sub.13 C.sub.6     H.sub.13 CH.sub.3 C.sub.4 H.sub.9 C.sub.4 H.sub.9 C.sub.4 H.sub.9     C.sub.4 H.sub.9 2,4-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3 CH.sub.2 H 6-F 43     C.sub.6 H.sub.5 CH.sub.2 C.sub.2 H.sub.5 C.sub.6 H.sub.13 O F CH.sub.3 O     4-CH.sub.3 OC.sub.6 H.sub.4 CH.sub.2 C.sub.2 H.sub.5 C.sub.6 H.sub.13     C.sub.6 H.sub.5 5-CH.sub.3 O 44 C.sub.8 H.sub.17 C.sub.8 H.sub.17     C.sub.12 H.sub.25 Br C.sub.2 H.sub.5 C.sub.6 H.sub.5 CH.sub.3 3-NO.sub.2     C.sub.6 H.sub.4 CH.sub.2 CH.sub.3 6-CH.sub.3 O 45 C.sub.4 H.sub.9     C.sub.4 H.sub.9 C.sub.4 H.sub.9 C.sub.12 H.sub.25 CH.sub.3 4-CH.sub.3     C.sub.6 H.sub.5 C.sub.2 H.sub.5 C.sub.8 H.sub.17 C.sub.2 H.sub.5     H

It is contemplated that by following the procedure similar to thatdescribed in Example 8 above but employing the appropriately substituted2-R² -4-N-R-N-R¹ aminobenzaldehyde with the appropriately substituted1-(1-R⁷ -2-R⁸ -5/6-R⁹ -indol-3-yl)-1-(1-R¹³ -2-R¹⁴ -5/6-R¹⁵-indol-3-yl)ethene and sodium 4-R³ -benzenesulfinate there will beobtained the appropriate 1-(1-R⁷ -2-R⁸ -5/6-R⁹ -indol-3-yl)-1-(1-R¹³-2-R¹⁴ -5/6-R¹⁵ -indol-3-yl)-3-(2-R² -4-N-R-N-R¹ -aminophenyl)-3-(4-R³-benzenesulfonyl)propene of Formula IV, Examples 46 to 63 presented inTable III hereinbelow.

                                      TABLE III                                   __________________________________________________________________________    1-(1-R.sup.7 --2-R.sup.8 --5/6-R.sup.9 --indol-3-yl)-1-(1-R.sup.13            --2-R.sup.14 --5/6-R.sub.15--indol-3-yl-3-                                    (2-R.sup.2 --4-N--R--B--R.sup.1 --aminophenyl)-3-(4-R.sup.3 -benzenesulfon    yl)propene                                                                    EX.                                                                              R         R.sup.1                                                                           R.sup.2                                                                            R.sup.3                                                                           R.sup.7                                                                              R.sup.8                                                                          R.sup.9                                                                              R.sup.13                                                                           R.sup.14                                                                         R.sup.15                   __________________________________________________________________________    46 C.sub.4 H.sub.9                                                                         C.sub.4 H.sub.9                                                                   C.sub.4 H.sub.9                                                                    C.sub.12 H.sub.25                                                                 H      CH.sub.3                                                                         H      H    CH.sub.3                                                                         H                          47 C.sub.8 H.sub.17                                                                        C.sub.8 H.sub.17                                                                  C.sub.12 H.sub.25                                                                  Br  H      C.sub.6 H.sub.5                                                                  H      H    C.sub.6 H.sub.5                                                                  H                          48 C.sub.6 H.sub.5 CH.sub.2                                                                C.sub.2 H.sub.5                                                                   C.sub.6 H.sub.13 O                                                                 F   C.sub.6 H.sub.5 CH.sub.2                                                             H  5-F    C.sub.6 H.sub.5 CH.sub.2                                                           H  5-F                        49 C.sub.6 H.sub.13                                                                        C.sub.6 H.sub.13                                                                  CH.sub.3                                                                           C.sub.4 H.sub.9                                                                   CH.sub.3                                                                             H  6-NO.sub.2                                                                           CH.sub.3                                                                           H  6-NO.sub.2                 50 4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2                                                     H   C.sub.3 H.sub.7                                                                    C.sub. 2 H.sub.5                                                                  C.sub.8 H.sub.17                                                                     CH.sub.3                                                                         H      C.sub.8 H.sub.17                                                                   CH.sub.3                                                                         H                          51 4-ClC.sub.6 H.sub.4 CH.sub.2                                                            CH.sub.3                                                                          C.sub.4 H.sub.9                                                                    Cl  C.sub.4 H.sub.9                                                                      C.sub.2 H.sub.5                                                                  5-Br   C.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                                                                  5-Br                       52 4-CH.sub.3 C.sub.6 H.sub.4 CH                                                           C.sub.3 H.sub.7                                                                   NO.sub.2                                                                           C.sub.4 H.sub.9                                                                   C.sub.4 H.sub.9                                                                      H  5-CH.sub.3 O                                                                         C.sub.4 H.sub.9                                                                    H  5-CH.sub.3 O               53 C.sub.12 H.sub.25                                                                       C.sub.12 H.sub.25                                                                 Cl   C.sub.3 H.sub.7                                                                   H      C.sub.2 H.sub.5                                                                  5-CH.sub.3                                                                           H    C.sub.2 H.sub.5                                                                  5-CH.sub.3                 54 C.sub.16 H.sub.33                                                                       C.sub.16 H.sub.33                                                                 Br   Br  CH.sub.3                                                                             H  5-Br--6-NO.sub.2                                                                     CH.sub.3                                                                           H  5-Br--6-NO.sub.2           55 C.sub.6 H.sub.5 CH.sub.2                                                                C.sub.4 H.sub.9                                                                   CH.sub.3                                                                           C.sub.12 H.sub.25                                                                 H      CH.sub.3                                                                         5,6-(CH.sub.3).sub.2                                                                 H    CH.sub.3                                                                         5,6-(CH.sub.3).sub.2       56 2,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2                                           H   C.sub.8 H.sub.17 O                                                                 C.sub.2 H.sub.5                                                                   C.sub.12 H.sub.25                                                                    CH.sub.3                                                                         H      C.sub.12 H.sub.25                                                                  CH.sub.3                                                                         H                          57 C.sub.6 H.sub.5                                                                         C.sub.2 H.sub.5                                                                   C.sub.4 H.sub.9                                                                    H   C.sub.16 H.sub.33                                                                    CH.sub.3                                                                         H      H    CH.sub.3                                                                         6-Br                       58 4-CH.sub.3 C.sub.6 H.sub.5                                                              CH.sub.3                                                                          C.sub.2 H.sub.5                                                                    C.sub.4 H.sub.9                                                                   H      C.sub.6 H.sub.5                                                                  6-Cl   H    C.sub.2 H.sub.5                                                                  6-CH.sub.3                 59 4-CH.sub.3 OC.sub.6 H.sub.4                                                             C.sub.2 H.sub.5                                                                   NO.sub.2                                                                           C.sub.2 H.sub.5                                                                   4-BrC.sub.6 H.sub.4 CH.sub.2                                                         CH.sub.3                                                                         H      C.sub.2 H.sub.5                                                                    CH.sub.3                                                                         H                          60 3-NO.sub.2 C.sub.6 H.sub.4 CH.sub.2                                                     H   F    C.sub.8 H.sub.17                                                                  C.sub.6 H.sub.13                                                                     C.sub.3 H.sub.7                                                                  6-CH.sub.3                                                                           C.sub.6 H.sub.13                                                                   C.sub.3 H.sub.7                                                                  6-CH.sub.3                 61 C.sub.14 H.sub.29                                                                       C.sub.14 H.sub.29                                                                 Cl   NO.sub.2                                                                          3-ClC.sub.6 H.sub.4 CH.sub.2                                                         C.sub.2 H.sub.5                                                                  H      C.sub.2 H.sub.5                                                                    CH.sub.3                                                                         H                          62 C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5                                                                   CH.sub.3                                                                           Cl  C.sub.6 H.sub.5 CH.sub.2                                                             H  5-F    C.sub.6 H.sub.5 CH.sub.2                                                           H  5-F                        63 3-NO.sub.2 C.sub.6 H.sub.4                                                              CH.sub.3                                                                          CH.sub.3 O                                                                         C.sub.12 H.sub.25                                                                 C.sub.10 H.sub.21                                                                    CH.sub.3                                                                         H      C.sub.10 H.sub.                                                                    CH.sub.3                                                                         H                          __________________________________________________________________________

EXAMPLE 64

The use of compounds of Formulas I, II, III, and IV, described in theforegoing examples, as color-forming components in pressure-sensitivemicroencapsulated copying systems is illustrated by the incorporationand testing of the compound of Example 1,1,1-bis(4-N,N-dimethylaminophenyl)-3-(4-N,N-dimethylaminophenyl)-3-(4-methylbenzenesulfonyl)prop-1-enein a pressure-sensitive marking paper. The test paper was prepared by aprocedure similar to that described in U.S. Pat. No. 4,275,905.

A. A mixture of 7.8 g of 10 percent aqueous EMA 31 (ethylene maleicanhydride copolymer with a molecular weight range of 75,000 to 90,000,supplied by Monsanto Chemical Co.), 14.5 g of 10 percent aqueous EMA1104 (ethylene maleic anhydride copolymer with a molecular weight rangeof 5,000 to 7,000, supplied by Monsanto Chemical Co.), 78.0 ml ofdistilled water was adjusted to pH 4.0 with the addition of 25 percentaqueous sodium hydroxide. A solution was prepared by dissolving 1.2 g of1,1-bis(4-N,N-dimethylaminophenyl)-3-(4-N,N-dimethylaminophenyl)-3-(4-methylbenzenesulfonyl)prop-1-enein 58.8 g of an alkylbenzene. This solution was added to the aqueousmixture and the resulting mixture was emulsified using a variable speedone-half horsepower Eppenbach Homomixer (Gifford Wood Co., Hudson, NY)at an applied voltage of 60 volts until droplets are smaller than 5microns. While maintaining the rapid agitation, 22.5 g of 50 percentaqueous Resimene 714 (methylated methylol melamine resin, supplied byMonsanto Chemical Co.) was added over approximately three to fiveminutes. After the microcapsules had formed, the suspension wastransferred to a round bottom flask equipped with a conventionalblade-type laboratory agitator and stirred approximately two hours at50° C. The mixture was then stirred overnight at ambient temperature.The mixture was adjusted to pH 7.0 with the addition concentratedaqueous sodium hydroxide.

A. the microcapsule suspension prepared in part A above was coated onpaper sheets to a thickness of approximately 0.0015 inch and the coatedsheets of paper air dried. The paper thus coated with themicroencapsulated colorless precursor was assembled as the top sheet ina manifold system by positioning the coated side in contact with a colordeveloper of the electron-accepting type. More specifically, paperscoated with a phenolic resin, organic and or with an acidic clay wereemployed in this test. An image was then drawn with a stylus on the topsheet bearing the microencapsulated colorless precursor on its reverseside causing the effected microcapsules to rupture thus allowing thesolution of the colorless precursor held by said microcapsules to flowinto contact with the color-developing substance on the receiving sheetwhereupon a color image immediately formed. On the acidic clay receivingsheet the image was a blue color. On the phenolic resin receiving sheetthe image was a blue color. Both developed images exhibited excellentlight stability and near infrared absorption when developed at 775 nm.

EXAMPLE 65

The utility of the compounds of Formulas I, II, III, and IV ascolor-forming components in thermal marking systems is illustrated bythe incorporation and testing of the compound of Example 1,1,1-bis(4-N,N-dimethylaminophenyl)-3-(4-N,N-dimethylaminophenyl)-3-(4-methylbenzenesulfonyl)propenein a thermal-responsive marking paper. The test paper was prepared by aprocedure similar to that described in U.S. Pat. No. 3,539,375.

A. A mixture of 2.0 g of1,1-bis(4-N,N-dimethylaminophenyl)-3-(4-N,N-dimethylaminophenyl)-3-(4-methylbenzenesulfonyl)propeneof a 10 percent aqueous solution of polyvinyl alcohol (approximately 99percent hydrolyzed), 8.6 g of distilled water and 31.6 g of 1/16 inchdiameter zirconium grinding beads was charged into a container which wasplaced in a mechanical shaker. Shaking was effected for one hour. Thezirconium beads were then removed by straining the mixture through a No.40 sieve.

B. Similarly, a mixture of 9.8 g of 4,4'-isopropylidine diphenol(Bisphenol A), 42.0 g of a 10 percent aqueous polyvinyl alcohol solution(approximately 99 percent hydrolyzed), 18.2 g of water and 221.1 g of1/16 inch diameter zirconium grinding beads was charged into a containerwhich was placed in a mechanical shaker. After shaking was effected forone hour, the zirconium beads were removed by straining through a No. 40sieve.

C. A coating composition was prepared by mixing 2.5 g of the slurry fromPart A and 22.5 g of the slurry from Part B. The mixture was thenuniformly coated on sheets of paper at a thickness of approximately0.0015 inch and the coated sheets air dried. The coated paper placed ona smooth flat surface with a stylus heated to approximately 125° C. Anintense cyan-colored image corresponding to the traced design promptlydeveloped.

What is claimed is:
 1. A 1-A-1-B-3-(2-R² -4-N-R-N-R¹-aminophenyl)-3-(4-R³ -phenylsulfonyl)prop-1-ene having the formula##STR9## wherein: A represents a moiety selected from the groupconsisting of ##STR10## B represents a moiety selected from the groupconsisting of ##STR11## in which: Z, represents-NR¹¹ R¹² ; R, R⁵ and R¹¹independently represent hydrogen; non-tertiary C₁ to C₁₆ alkyl; phenyl;phenyl substituted by one or two of non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy, nitro or halo; benzyl; or benzylsubstituted in the benzene ring by one or two of non-tertiary C₁ to C₄alkyl, non-tertiary C₁ to C₄ alkoxy, nitro or halo;R¹, R⁶ and R¹²independently represent non-tertiary C₁ to C₁₆ alkyl; R², R⁴ and R¹⁰independently represent hydrogen, non-tertiary C₁ to C₁₆ alkyl,non-tertiary C₁ to C₈ alkoxy, nitro or halo; R³ represents hydrogen,non-tertiary C₁ to C₁₆ alkyl, non-tertiary C₁ to C₄ alkoxy, nitro orhalo; R⁷ and R¹³ independently represent hydrogen; or non-tertiary C₁ toC₁₆ alkyl unsubstituted or substituted by non-tertiary C₁ to C₁₆ alkoxy,phenoxy, phenyl, phenyl substituted by one or two of non-tertiary C₁ toC₄ alkyl, non-tertiary C₁ to C₄ alkoxy, nitro or halo; R⁸ and R¹⁴independently represent hydrogen, non-tertiary C₁ to C₄ alkyl or phenyl;and R⁹ and R¹⁵ independently represent one or two of hydrogen,non-tertiary C₁ to C₄ alkyl, non-tertiary C₁ to C₄ alkoxy, nitro orhalo, and wherein R and R¹ together with the nitrogen can representpiperdinyl or pyrrolidinyl.
 2. A 1-(2-R⁴ -N-R⁵ -N-R⁶-aminophenyl)-1-(2-R¹⁰ -4-N-R¹¹ -N-R¹² -aminophenyl)-3-(2-R² -4-N-R-N-R¹-aminophenyl)-3-(4-R³ -phenylsulfonyl)prop-1-ene according to claim 1wherein A is (2-R⁴ -4-N-R⁵ -N-R⁶ -aminophenyl) and B is (2-R¹⁰ -4-N-R¹¹-N-R¹² -aminophenyl) in which R, R¹, R², R³, R⁴, R⁵, R⁶, R¹⁰, R¹¹, andR¹² have the same respective meanings given in claim
 1. 3. A propeneaccording to claim 2 selected from the group consisting of1,1,3-tris(4-dimethylaminophenyl)-3-(4-methylphenylsulfonyl)prop-1-ene;1,1-bis(4-dimethylaminophenyl)-3-(4-dimethylaminophenyl)-3-(4-methylphenylsulfonyl)prop-1-ene;1,1-bis(4-dimethylaminophenyl)-3-(4-diethylaminophenyl)-3-(4-methylphenylsulfonyl)prop-1-ene;1,1-bis(4-dimethylaminophenyl)-3-(4-piperidinylphenyl)-3-(4-methylphenylsulfonyl)prop-1-ene;1-phenyl-1-bis(4-dimethylaminophenyl)-3-(4-methylphenylsulfonyl)prop-1-ene;and1,1-bis(4-dimethylaminophenyl)-3-(2-methyl-4-diethylaminophenyl)-3-(4-methylphenylsulfonyl)prop-1-ene.4. A 1-(2-R⁴ -4-N-R⁵ -N-R⁶ -aminophenyl)-1-(1-R¹³ -2-R¹⁴ -5/6-R¹⁵-indol-3-yl)-3-(2-R² -4-N-R-N-R¹ -aminophenyl)-3-(4-R³-phenylsulfonyl)prop-1-ene according to claim 1 wherein A is (2-R⁴-4-N-R⁵ -N-R⁶ -aminophenyl) and B is (1-R¹³ -2-R¹⁴ -5/6-R¹⁵ -indol-3-yl)in which R, R¹, R², R³, R⁴, R⁵, R⁶, R¹³, R¹⁴, and R¹⁵ have the samerespective meanings given in claim
 1. 5.1-(4-Dimethylaminophenyl)-1-(1-octyl-2-methylindol-3-yl)-3-(4-diethylaminophenyl)-3-(4-methylphenylsulfonyl)prop-1-eneaccording to claim
 4. 6. A 1-(1-R⁷ -2-R⁸ -5/6-R⁹ -indol-3-yl)-1-(1-R¹³-2-R¹⁴ -5/6-R¹⁵ -indol-3-yl)-3-(2-R² -4-N-R-N-R¹-aminophenyl)-3-(4-methylphenylsulfonyl)prop-1-ene according to claim 1wherein A is (1-R⁷ -2-R⁸ -5/6-R⁹ -indol-3-yl) and B is (1-R¹³ -2-R¹⁴-5/6-R¹⁵ -indol-3-yl) in which R, R¹, R², R³, R⁷, R⁸, R⁹, R¹³, R¹⁴, andR¹⁵ have the same respective meanings given in claim
 1. 7.1,1-Bis(1-ethyl-2-methylindol-3-yl)-3-(4-dimethylaminophenyl)-3-(4-methylphenylsulfonyl)prop-1-eneaccording to claim 6.